EP2846900B1 - Membranbasierte verfahren zur selektiven fraktionierung von ätherischen ölen - Google Patents

Membranbasierte verfahren zur selektiven fraktionierung von ätherischen ölen Download PDF

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EP2846900B1
EP2846900B1 EP13711664.6A EP13711664A EP2846900B1 EP 2846900 B1 EP2846900 B1 EP 2846900B1 EP 13711664 A EP13711664 A EP 13711664A EP 2846900 B1 EP2846900 B1 EP 2846900B1
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Prior art keywords
oil
membrane
essential oil
mol
essential
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English (en)
French (fr)
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EP2846900A1 (de
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Xiaoping Wu
Andrew Boam
Andrea MENICONI
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Evonik Operations GmbH
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Evonik Operations GmbH
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Priority to EP20159295.3A priority Critical patent/EP3677328A1/de
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/02—Recovery or refining of essential oils from raw materials
    • C11B9/025—Recovery by solvent extraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
    • B01D71/701—Polydimethylsiloxane
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/02—Recovery or refining of essential oils from raw materials
    • C11B9/022—Refining
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes

Definitions

  • the present disclosure in general relates to a process for (1) reducing impurities, i.e. undesirable natural components such as waxes and undesirable synthetic materials such as agrochemicals and other environmental pollutants, or (2) fractionation of natural components present in an essential oil using at least one selective nanofiltration membrane.
  • impurities i.e. undesirable natural components such as waxes and undesirable synthetic materials such as agrochemicals and other environmental pollutants
  • fractionation of natural components present in an essential oil using at least one selective nanofiltration membrane.
  • Essential oils are produced from plant materials through three main routes, distillation, extraction with a suitable hydrophobic solvent and expression (physical crushing) depending on the location of the oil within the plant material and the inherent properties of the oil. In all cases the production technique generates a solution containing a mixture of compounds. In many cases the essential oil must be removed from a second aqueous phase that is present as a result of the production process. Furthermore, the valuable components of the oil must often be further separated from unwanted materials present in produced oil to generate the final desired product.
  • Essential oils including citrus oils, contain a broad range of high value chemical species, many of which have valued organoleptic properties that are used in the food and beverage industry, and the flavour and fragrance industry for example.
  • Natural impurities include components that form solid "wax" material either after extended period of standing or when the oil is cooled, these include but are not limited to high molecular weight hydrocarbons or esters, coumarins, sterols, flavonoids, etc.
  • synthetic impurities that may be present in the crude oil and these include but are not limited to organic compounds extracted from packaging materials (e.g. phthalates) and agrochemicals (e.g. insecticides, fungicides, etc.).
  • Aqueous chemical washes only target species in the crude oil that can be ionized to form salts with components in the aqueous solution for example see EP0656932 and US2007237844A1 ), these salts are insoluble in the crude essential oil, and the salt form of the impurity is removed to the aqueous wash solution - thus reducing the concentration of the impurity in the crude essential oil.
  • this approach is only efficient for impurity compounds that can be ionized or can be extracted into an aqueous phase.
  • Dupuy et al. (Journal of Membrane Science 378 (2011), 203- 213 , and Flavour and Fragrance Journal 26 (2011), 192-203 ) also report the application of membranes in the form of membrane contactors to provide emulsion-free extraction of essential oil components from lemon oil into aqueous ethanolic solutions. In this process, the quality of separation is governed by the aqueous ethanolic extraction solvent and not the membrane properties. The membrane stabilizes the interface between the lemon oil and the aqueous ethanolic solution.
  • EP2205710 to Givaudan describes a membrane-based process to dewax citrus oils.
  • the process described in the patent utilises either ultrafiltration or microfiltration membranes to remove wax compounds from citrus oils, such that they do not generate further solid wax when left to stand at 4 degC for 48 hours.
  • the citrus oil is chilled to about 10 degC prior to filtration to enhance the ease with which the wax compounds can be filtered.
  • Essential oils encompass a very broad range of non-lipid natural oils derived from plant matter, e.g. citrus oils, rosemary oil, lemongrass oil, lavender oil, eucalyptus oil, etc.
  • crude essential oils contain the desired essential oil components (e.g. terpenic hydrocarbons, aldehydes, alcohols, esters, etc.) as well as a range of unwanted impurities - for instance wax compounds (often associated with the cuticle of the feedstock), agrochemical residues (from the farming of the feedstock).
  • desired essential oil components e.g. terpenic hydrocarbons, aldehydes, alcohols, esters, etc.
  • unwanted impurities e.g. terpenic hydrocarbons, aldehydes, alcohols, esters, etc.
  • unwanted impurities e.g. terpenic hydrocarbons, aldehydes, alcohols, esters, etc.
  • unwanted impurities e.g. terpenic hydrocarbons, alde
  • a special problem of the present invention was to provide a process which may achieve the combined effect of one, two, three or more of the conventional processing steps applied to essential oils (for instance dewaxing, colour removal (adsorption), fractionation, agrochemical removal) in a single process.
  • the disclosed process should therefore simplify and/or speed up the production of an essential oil and potentially improve oil yield and quality.
  • Another problem was to provide a flexible process which allows to remove impurities from an essential oil and/or to be used for fractionating at least one component of the oil, resulting in the formation of an enriched concentrate solution of the at least one natural component. This may lead to the production of new products.
  • a special problem of the present invention was to provide a process to purify essential oils in a more economical way from wax and synthetic impurities while avoiding as much as possible negative effects on the flavour/fragrance profile of the essential oil product.
  • the present disclosure relates to a process for (1) reducing impurities, i.e. undesirable natural components such as waxes and undesirable synthetic materials such as agrochemicals and other environmental pollutants, or (2) fractionation of natural components present in an essential oil comprising contacting the essential oil with at least one selective nanofiltration membrane, wherein a retentate is formed comprising at least one compound from the essential oil and a permeate forms comprising at least one compound from the essential oil such that the composition of the retentate and permeate is different.
  • impurities i.e. undesirable natural components such as waxes and undesirable synthetic materials such as agrochemicals and other environmental pollutants
  • fractionation of natural components present in an essential oil comprising contacting the essential oil with at least one selective nanofiltration membrane, wherein a retentate is formed comprising at least one compound from the essential oil and a permeate forms comprising at least one compound from the essential oil such that the composition of the retentate and permeate is different.
  • nanofiltration membranes have much better dewaxing properties compared to ultrafiltration or microfiltration membranes.
  • the test for successful dewaxing applied by Givaudan (standing for 48 hours at 4 degC) is too mild to define successful dewaxing.
  • Dewaxing a citrus oil with the process of the invention, versus an ultrafiltration membrane of Givaudan, when applying a more rigorous -20 degC dewaxing test shows, that at -20 degC a solution from an ultrafiltration process is cloudy, whereas solutions produced according to the invention are transparent.
  • Another unexpected advantage of the present invention was that sufficient flux, up to at least 5 L.m -2 .h -1 could be realized. This is beneficial for an economic process.
  • the process of the invention allows to save process steps and even though synthetic impurities have a molecular weight ⁇ 500 Da, it allows to simultaneously dewax and remove synthetic impurities. This is another important and unexpected advantage.
  • essential oil shall be taken to mean hydrophobic oils derived from plant matter, that contain less than 40 % by weight, preferably less than 30 % by weight, particular preferred less than 20 % by weight, very particular preferred less than 10 % by weight, especially preferred less than 5 % by weight, very especially preferred less than 1 % by weight and most preferred 0 % by weight of lipids or lipid oils.
  • Lipids are compounds based on fatty acids and derivatives of fatty acids.
  • Lipid oils are defined to be oils based on fatty acids and derivates of fatty acids (such as glyceride oils), whereas many essential oils have a base of terpene hydrocarbons.
  • essential oils examples include citrus oils, mint oils, cedarwood oil, eucalyptus oil, clove oil, etc.
  • vegetable lipid oils examples include sunflower oil, olive oil, peanut oil, soya oil, corn oil, etc.
  • essential oil shall also be taken to encompass mixtures of more than one "essential oil”.
  • an essential oil is a concentrated, hydrophobic liquid containing volatile aroma compounds extracted from plants.
  • Essential oils are composed primarily of terpenes and of lesser quantities of alcohols, aldehydes, esters, phenols, and other compounds that impart particular odours or flavours. They are usually obtained from plants, leaves, flowers, roots, buds, twigs, rhizomes, heartwood, bark, resin, seeds and fruits.
  • Essential Oils are usually found in special secretory glands or cells within the plants. The aromatic substances are formed and stored in certain organs of a plant as a by-product or because of its metabolism.
  • Each essential oil contains its own blueprint of chemical entities that is absolutely unique to that specific oil.
  • Essential oils as used for feed-stock in the present invention are produced by distillation, expression, or solvent extraction with supercritical solvents.
  • Essential oils are used in perfumery, aromatherapy, cosmetics, incense, medicine, household cleaning products, and for flavouring food and drink. They are valuable commodities in the fragrance and food industries. They are not to be confused with essential fatty acids or with plant extracts prepared with more polar solvents comprising only the more polar components of the essential oil.
  • essential oils are oils according to ISO 9235, i.e. are products obtained from a natural raw material of plant origin:
  • essential oils encompass the essential oils according to the first preferred embodiment and also essential oils that may be obtained by mechanical expression from plants material other than Citrus fruits.
  • essential oils encompass the essential oils of the first and second preferred embodiment and also essential oils that are obtained by extraction of the plant material with supercritical solvents, preferably supercritical CO 2 .
  • crude products are obtained after extraction of the plant material with the solvent.
  • these extracts are called “concrete” and may contain significant amounts of waxes, resins and other lipophilic plant material.
  • crude essential oils or pre-purified essential oil obtained by the processes described above can be used as feed-stock for the process of the present invention.
  • fatty acid(s) includes for example short-chain and long-chain saturated and unsaturated (e.g., monounsaturated and polyunsaturated) hydrocarbons comprising one carboxylic acid group.
  • Derivatives of fatty acids include fatty acid esters, glycerides, phosphoesters, etc.
  • fractionation shall be understood to mean that the concentration of a given species in solution is different in the retentate and permeate solutions generated by applying the process described herein. It will be understood by one skilled in the art that this means a given species could "fractionate” into either the permeate or retentate solutions, and furthermore that "fractionation” as defined here can incorporate enrichment, depletion, complete removal and complete capture of a species in either the retentate of permeate solutions.
  • Nanofiltration as used in this disclosure shall be taken to mean a synthetic membrane that provides a nominal molecular weight cut-off in the range 150 g.mol -1 to 1,500 g.mol -1 , where nominal molecular weight cut-off means the molecular weight at which the membrane provides a 90% rejection of a series of polystyrene oligomers (for example polystyrene polymer standards nominal Mp of 1,000 (part number PL2012-3010 ) and nominal Mp 580 (part number PL2012-2010 ) from Agilent Technologies) according to the method described in See Toh et al, (Journal of Membrane Science, 291(1-2) (2007), 120-125 ). Nanofiltration membranes differ from ultrafiltration membranes (molecular weight cut-off in the range 2,000 Da to 2,000,000 Da) and microfiltration membranes (pore diameter 0.2 micron and larger).
  • natural impurity shall be taken to mean any chemical species that is naturally occurring in the feedstock, but which is not a desired species in the final form of the essential oil. Typical examples can include waxes (as they may lead to undesirable cloudiness in the oil product), colour compounds (which may not be desired if the oil is to be blended into a product of a different colour), sterols and vitamins.
  • synthetic impurity as used in this disclosure shall be taken to mean any chemical species that is not naturally occurring in the feedstock from which the essential oil is produced. It will be understood by one skilled in the art that synthetic impurity can incorporate both man-made and naturally occurring compounds that are applied as agrochemicals or are present as environmental pollutants.
  • wax as used in this disclosure shall be taken to mean naturally occurring species in the essential oil that are able to impart cloudiness to the oil product at temperatures below 20 degC.
  • Typical wax compounds found in essential oils include long-chain aliphatic hydrocarbons (typically C14 or longer), long-chain alcohols (typically C14 or longer), and related ketones, aldehydes, acids, diols, etc., and coumarins, sterols, flavonoids.
  • an essential oil according to the present disclosure is derived from plant matter.
  • the essential oil may comprise of a mixture of more than one essential oil.
  • the essential oil may derive from several different parts of the plant, including by way of non-limiting example berries, seeds, bark, wood, rhizome, leaves, resin, flowers, peel and root.
  • Preferred essential oils are derived from the genus Citrus. Particular preferred essential oils are selected from oils deriving from sweet orange, orange, lemon, lime, grapefruit, bergamot, key lime, pomelo, citron, mandarin, tangerine, bitter orange, rangpur, Persian lime, Clementine, yuzu, kaffir lime, ugli.
  • Essential oils include by way of non-limiting example allspice oil, juniper oil, cumin oil, cinnamon bark oil, camphor oil, rosewood oil, ginger oil, basil oil, eucalyptus oil, lemongrass oil, peppermint oil, rosemary oil, spearmint oil, tea tree oil, frankincense oil, chamomile oil, clove oil, jasmine oil, lavender oil, rose oil, ylang ylang oil, bergamot oil, grapefruit oil, lemon oil, lime oil, orange oil, and valerian oil.
  • Essential oils are a rich source of a wide variety of natural compounds that have found numerous applications. Bakkali et al. (Food and Chemical Toxicology 46 (2008) 446-475 ) review the many uses of essential oils - these include bactericidal, virucidal, fungicidal, antiparasitical, insecticidal, medicinal, cosmetic, and flavour/fragrance applications. For example, many components in essential oils alter the composition of the cell wall of common bacterial/fungal pathogens which may be lethal to the microorganism or make it much easier for other antimicrobial compounds to function. A further example of the benefits of essential oils includes their antioxidant and prooxidant capabilities, which can help protect cells but also eliminate damaged cells through enhancing apoptosis.
  • a number of essential oils also contain compounds with potent pharmaceutical activities. These include artemisinin, which is an anitmalarial compound derived from Artemisia annua, hyperforin, which is an antidepressant drug derived from Hypericum perforatum, as well as various sterols (" Supercritical Fluid Extraction of Nutraceuticals and Bioactive Compounds", ed. J.L. Martinez (2008) ISBN 978-0-8493-7089-2 ).
  • Suitable selective membranes for use according to the present disclosure include polymeric and ceramic membranes, and mixed polymeric/inorganic membranes.
  • the at least one selective membrane used in the process of the present invention may be formed from any polymeric or ceramic material which provides a separating layer capable of fractionating the essential oil content or separating the desired essential oil content from at least one natural and/or synthetic impurity present in the essential oil.
  • the at least one selective membrane may be formed from or comprise a material chosen from polymeric materials suitable for fabricating nanofiltration membranes, including preferably polyethylene, polypropylene, polytetrafluoroethylene (PTFE), polyvinylidene difluoride (PVDF), polysulfone, polyethersulfone, polyacrylonitrile, polyamide, polyimide, polyamideimide, polyetherimide, cellulose acetate, polyaniline, polypyrrole, polyetheretherketone (PEEK), polybenzimidazole, and mixtures thereof.
  • the at least one selective membrane can be made by any technique known to the art, including sintering, stretching, track etching, template leaching, interfacial polymerization, or phase inversion.
  • the at least one selective membrane may be crosslinked or treated so as to improve its stability in the reaction solvents.
  • the membranes described in GB2437519 the contents of which are incorporated herein by reference, may be used in this disclosure.
  • the at least one selective membrane is a crosslinked or none crosslinked composite material comprising a support and a thin, selectively permeable layer.
  • the thin, selectively permeable layer may, for example, be formed from or comprise a material chosen from modified polysiloxane based elastomers including polydimethylsiloxane (PDMS) based elastomers, ethylene-propylene diene (EPDM) based elastomers, polynorbornene based elastomers, polyoctenamer based elastomers, polyurethane based elastomers, butadiene and nitrile butadiene rubber based elastomers, natural rubber, butyl rubber based elastomers, polychloroprene (Neoprene) based elastomers, epichlorohydrin elastomers, polyacrylate elastomers, polyethylene, polypropylene, polytetra
  • At least one selective nanofiltration membrane or nanofiltration composite membrane comprising a polyimide
  • a polyimide particular preferred is a polyimide subject to post-formation crosslinking and impregnation with a low volatility compound.
  • a polyimide particularly preferred are polyimides according to GB2437519 and Soroko et al. (Journal of Membrane Science, 381(1-2) (2011), 152-162 ) the contents of which are incorporated herein by reference.
  • silicone-coated organic solvent nanofiltration membranes especially on the basis of polyimide nanofiltration membranes.
  • Most particular preferred membranes as for example described in DE10 2009 07 351 or disclosed in International Patent Application WO2012010889 , may be used in this disclosure.
  • the inventors found out that especially when using silicone-coated organic solvent nanofiltration membranes dewaxing and reduction in concentration of certain synthetic impurities can be performed at ambient and above-ambient temperature conditions without the membrane fouling or the organoleptic properties of the essential oil being affected.
  • the silicone coating minimizes deposition of waxy compounds on the membrane surface, thus minimizing fouling which leads to stable membrane performance over time.
  • silicone coated membranes seem to achieve compared to uncoated membranes is, that the solution-diffusion nature of mass transport in silicone coatings means that these membranes offer discrimination between the essential oil components and certain synthetic impurities of similar molecular weight that is not achieved to this degree with phase inversion membranes.
  • the at least one selective membrane is prepared from an inorganic material such as, for example, silicon carbide, silicon oxide, zirconium oxide, titanium oxide, and zeolites, using any technique known to those skilled in the art such as sintering, leaching, or sol-gel processing.
  • an inorganic material such as, for example, silicon carbide, silicon oxide, zirconium oxide, titanium oxide, and zeolites, using any technique known to those skilled in the art such as sintering, leaching, or sol-gel processing.
  • the at least one selective membrane comprises a polymer membrane with dispersed organic or inorganic matrices in the form of powdered solids present at amounts up to 20 wt% of the polymer membrane.
  • Carbon molecular sieve matrices can be prepared by pyrolysis of any suitable material as described in U.S. Patent No. 6,585,802 .
  • Zeolites as described in U.S. Patent No. 6,755,900 may also be used as an inorganic matrix.
  • Metal oxides, for example, titanium dioxide, zinc oxide, and silicon dioxide may be used, such as the materials available from Evonik Industries AG (Germany) under their AEROSIL and ADNANO trademarks.
  • the matrices will be particles less than 1.0 micron in diameter, for example less than 0.1 microns in diameter, such as less than 0.01 microns in diameter.
  • more than one membrane respectively more than one membrane separation step are comprised in the process of the invention.
  • two different membranes having two different molecular weight cut-offs are used.
  • Essential oils may contain undesirable natural impurities or undesirable synthetic impurities, that must be removed from the essential oil for its' desired use.
  • the disclosed method can effectively remove a wide range of natural and synthetic impurities, thereby producing oils suitable for their desired applications.
  • the process disclosed herein describes separating impurities from an essential oil, resulting in oil having impurity levels within desired and/or regulatory limits for, for instance, human consumption.
  • the concentration and composition of the impurities found in the essential oil can vary.
  • an essential oil composition may vary based on species from which the oil derives part of the plant from which the oil derives geographical location where the plant is grown, harvesting season, etc.
  • the targeted impurities may be absent or below the detection limit, but if the oil is concentrated, the impurities may also be concentrated.
  • the impurities present in the essential oil may be natural or synthetic impurities such as, by way of non-limiting example, environmental pollutants, agrochemical residues, extractables from packaging, plant sterols, lipohilic hormones, waxes, coloured components, oxidation products, vitamins, and components that create unwanted smell and taste in the oil, such as aldehydes and/or ketones.
  • the removal of coloured components results in an oil having improved colour
  • removal of components that create unwanted smell and taste result in an oil having an improved organoleptic profile.
  • environment pollutants includes, but is not limited to, for example, polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs), hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethane (DDT), dioxins, furans, non-ortho-PCBs, and metals.
  • PCBs polychlorinated biphenyls
  • PBDEs polybrominated diphenyl ethers
  • PAHs polycyclic aromatic hydrocarbons
  • HHs hexachlorocyclohexanes
  • DDT dichlorodiphenyltrichloroethane
  • dioxins furans, non-ortho-PCBs, and metals.
  • Chlorinated pesticides includes, for example, lindane, endrin, dieldrin, aldrin, isodrin, heptachlor-exo-epoxide, heptachlor-endo-epoxide, trans-chlordane, cis-chlordane, oxy-chlordane, chlordane, heptachlor, endosulfan-1, and mirex.
  • pesticide examples include organophosphorous pesticides, such as by way of non-limiting example parathion, malathion, methyl parathion, chlorpyrifos, diazinon, dichlorvos, phosmet, fenitrothion tetrachlorvinphos, and azinphos methyl, and carbamate pesticids, such as by way of non-limiting example aldicarb, carbofuran (Furadan), carbaryl (Sevin), ethienocarb, and fenobucarb.
  • organophosphorous pesticides such as by way of non-limiting example parathion, malathion, methyl parathion, chlorpyrifos, diazinon, dichlorvos, phosmet, fenitrothion tetrachlorvinphos, and azinphos methyl
  • carbamate pesticids such as by way of non-limiting example aldicarb, carbofuran (Furadan), carbaryl (S
  • Natural impurities may include by way of non-limiting example, sterols, lipophilic hormones, and natural colours, for instance belonging to the carotenoids.
  • Extractables from packaging may include by way of non-limiting example compounds such as plasticisers (e.g. phthalates), unbound resin components, unbound oligomeric material from polymers, lubricants, etc.
  • Some embodiments of the present disclosure relate to a process for reducing impurities from an essential oil using at least one selective membrane. Additionally, some embodiments of the present disclosure relate to a process for fractionating at least one natural component from an essential oil using at least one selective membrane
  • fractionation of the undesirable natural and synthetic impurities may be achieved through contacting the oil solution with at least one selective membrane that retains the undesirable impurities, i.e., in the form of a retentate, and allows permeation of the desired essential oil compounds, i.e., in the form of a permeate.
  • Content permeates through the membrane due to, e.g., a trans-membrane pressure.
  • the trans-membrane pressure ranges from 1 to 100 bar.
  • the trans-membrane pressure may range from 5 to 75 bar, particular preferred 10 to 60 bar.
  • Fractionation of the essential oil may be achieved through contacting the oil solution with at least one selective membrane.
  • the essential oil is then fractionated with at least one species having a different concentration in the retentate solution than in the permeate solution.
  • Content permeates through the membrane due to, e.g., a trans-membrane pressure.
  • the trans-membrane pressure ranges from 1 to 100 bar.
  • the trans-membrane pressure may range from 5 to 75 bar, particular preferred 10 to 60 bar.
  • Reduction of the undesirable natural and synthetic impurities may be achieved through contacting the essential oil with at least one selective nanofiltration membrane that retains the undesirable impurities, i.e., in the form of a retentate, and allows permeation of the desired essential oil compounds, i.e., in the form of a permeate.
  • Content permeates through the membrane due to, e.g., a trans-membrane pressure.
  • the trans-membrane pressure ranges from 1 to 100 bar.
  • the trans-membrane pressure may range from 5 to 75 bar, particularly preferred 10 to 60 bar.
  • the present disclosure provides a process for reducing natural impurities (e.g. waxes, oxidation products, and colored components) and synthetic impurities (e.g. agrochemical residues, packaging extractables, etc.) present in an essential oil by applying membrane nanofiltration, comprising the steps of: (i) providing an essential oil ; (ii) providing at least one selectively permeable nanofiltration membrane having a first surface and a second surface; (iii) separating the oil from the impurities by transferring the essential oil from the first surface to the second surface across the at least one nanofiltration membrane(s) through contacting the essential oil with the first surface, wherein the pressure at the first surface is greater than the pressure at the second surface, and wherein the membrane(s) is/are selectively permeable membrane(s) such that the membrane rejection (R lmp ) of the impurities is greater than the rejection (R oil ) of the oil species.
  • natural impurities e.g. waxes, oxidation products, and colored components
  • the disclosed method can also be used to fractionate at least one natural component in the essential oil, such as one or more of the terpenic or oxygenated components of the essential oil, fat soluble vitamins, plant sterols, and/or colored components, using the disclosed selective nanofiltration membranes, resulting in the formation of a concentrate comprising the at least one natural component at a higher concentration than in the essential oil feedstock.
  • at least one natural component in the essential oil such as one or more of the terpenic or oxygenated components of the essential oil, fat soluble vitamins, plant sterols, and/or colored components
  • the fractionation is carried out by applying membrane nanofiltration, comprising the steps of: (i) providing an essential oil ; (ii) providing at least one selectively permeable nanofiltration membrane having a first surface and a second surface; (iii) separating the one or more components to be fractionated from the other components of the essential oil from by passing components from the first surface to the second surface across at least one nanofiltration membrane by contacting the essential oil with the first surface, wherein the pressure at the first surface is greater than the pressure at the second surface, and wherein the nanofiltration membrane(s) is/are selectively permeable membrane(s) such that the membrane rejection (R Comp ) of the components to be fractionated does not equal the rejection (R oil ) of the other oil components.
  • the process of the invention comprises subjecting the retentate oil and/or the permeate oil to at least one additional processing step, preferably at least one further membrane separation step.
  • a second stage further comprises providing the retentate from a first filtration that has been carried out to reduce the concentration of an impurity; passing the first retentate solution across at least one further selective membrane, preferably also a nanofiltration membrane, wherein a second retentate and a second permeate are formed wherein further impurity reduction has been carried out.
  • the process disclosed herein further comprises providing the permeate from a first filtration that has been carried out to reduce the concentration of an impurity; and passing the permeate solution across at least one further selective membrane, preferably also a nanofiltration membrane, wherein a second retentate and a second permeate are formed wherein further impurity reduction has been carried out
  • the processed essential oil may be treated with at least one adsorption process to remove additional components and/or remaining impurities.
  • the processed essential oil is treated with activated carbon, which, for example, may remove further environmental pollutants present in the essential oil.
  • the essential oil may be subject to additional separation processes to enhance the fractionation or remove additional impurities. Additional purification processes may include, for example, liquid-liquid extraction processes, fractional distillation, high pressure liquid chromatography, supercritical chromatography, or resin or ion exchange adsorption depending on the application.
  • Components of some essential oils are known to be vulnerable to thermal degradation. Compared to other known methods for the removal of natural and synthetic impurities, the method disclosed herein may be performed effectively at near-ambient or sub-ambient temperature conditions. Many of the other known methods of impurity removal involve higher temperatures, which may be harmful to the thermally-sensitive components, i.e. the thermally-sensitive components are converted to different chemical species which reduces their yield and may also change the organoleptic properties or efficacy of the essential oil.
  • the process of the present invention can preferably be carried out at 10 to 50 degC.
  • the disclosed method also relates to a process for reducing the amount of at least one component in an essential oil composition thus generating a concentrate of the at least one component.
  • the resulting concentrate(s) comprising at least one desired natural component may be used directly as a product in its own right, or it can be used as an intermediate that is subject to further separation processes, such as for instance chromatographic methods or crystallisation.
  • compositions resulting from the process disclosed herein may include the retentate, the purified oil, and/or the permeate material.
  • the disclosed process produces dewaxed essential oil.
  • the disclosed process produces a 90% reduction in at least one impurity, for example agrochemical residues, relative to the feed essential oil.
  • the colour of the essential oil is reduced for example from brown to pale yellow.
  • the essential oil is processed to reduce the concentration of impurities in the oil.
  • the disclosed process may produce a composition, such as the retentate, comprising an increased concentration of at least one of plant sterols, fumarocumarins, hormones, and natural colours, such as beta-carotene, compared to the feed essential oil.
  • the essential oil is processed to fractionate a component of the essential oil.
  • the disclosed process may produce a composition, such as the retentate, comprising an increased concentration of at least one of the components of the essential oil such as ⁇ -, ⁇ -sinensal or nootkatone, compared to the feed essential oil.
  • PuraMemTM S380 is a silicone-coated membrane prepared according to DE10 2009 047 351 with a nominal molecular weight cut-off of 600 g.mol -1 . The membrane was made ready for use by filtering 200 mL of limonene (Sigma-Aldrich, Germany) at ambient temperature and 30 bar filtration pressure to remove the conditioning agent (preservative) from the PuraMemTM S380 membrane.
  • the filtration cell was emptied and refilled with 100 mL of single-fold orange oil.
  • the single-fold orange oil was filtered at a temperature of 30 degC and filtration pressure of 30 bar. 75 mL of the oil was permeated and collected in 25 mL aliquots.
  • the strength of colour of the orange oil samples was determined using a UV spectrophotometer to measure the absorbance at a wavelength of 432 nm.
  • Figure 2 shows the measured UV absorbance of the feed oil, the retained portion of the orange oil and the three permeate aliquots.
  • the strength of colour in the permeate samples was reduced from approximately 16 absorbance units in the feed oil to approximately 1 absorbance unit in the permeate samples.
  • Concomitantly the strength of colour in the retentate increased from approximately 16 absorbance units to 23 absorbance units, which is consistent with only a small proportion of the coloured compounds being transported through the membrane during the filtration.
  • PuraMemTM S380 is a silicone-coated membrane prepared according to DE10 2009 047 351 with a nominal molecular weight cut-off of 600 g.mol -1 . The membrane was made ready for use by filtering 200 mL of limonene (Sigma-Aldrich, Germany) at ambient temperature and 30 bar filtration pressure to remove the conditioning agent (preservative) from the PuraMemTM S380 membrane.
  • the filtration cell was emptied and refilled with 100 mL of five-fold orange oil.
  • the five-fold orange oil was filtered at a temperature of 30 degC and filtration pressure of 30 bar. 65 mL of the oil was permeated; the first 25 mL permeate was collected as one aliquot "Permeate 1"; the next 20 mL of permeate was collected as a second aliquot ("Permeate 2"), and; the next 20 mL was collected as the third and final aliquot ("Permeate 3").
  • the strength of colour of the orange oil samples was determined using a UV spectrophotometer to measure the absorbance at a wavelength of 432 nm.
  • Figure 3 shows the measured UV absorbance of the feed oil, the retained portion of the orange oil and the three permeate aliquots.
  • the strength of colour in the permeate samples was reduced from approximately 85 absorbance units in the feed oil to 5-10 absorbance units in the permeate samples.
  • Concomitantly the strength of colour in retentate increased from approximately 85 absorbance units to 230 absorbance units, which is consistent with only a small proportion of the coloured compounds being transported through the membrane during the filtration.
  • PuraMemTM S380 is a silicone-coated membrane prepared according to DE10 2009 047 351 with a nominal molecular weight cut-off of 600 g.mol -1 . The membrane was made ready for use by filtering 200 mL of limonene (Sigma-Aldrich, Germany) at ambient temperature and 30 bar filtration pressure to remove the conditioning agent (preservative) from the PuraMemTM S380 membrane.
  • the filtration cell was emptied and refilled with 100 mL of five-fold orange oil.
  • the five-fold orange oil was filtered at a temperature of 30 degC and filtration pressure of 30 bar. 65 mL of the oil was permeated.
  • the wax content of the orange oil samples was determined after the oil samples had been chilled for at least 24 hours at -24 degC by assessing turbidity of the solutions using a UV spectrophotometer to measure the absorbance at a wavelength of 720 nm.
  • Figure 4 shows the measured UV absorbance of the feed oil, the retained portion of the orange oil and the permeated orange oil.
  • the wax content of the permeate samples was reduced from approximately 0.54 absorbance units in the feed oil to 0.18 absorbance units in the permeate samples.
  • Concomitantly the wax content of the retentate increased from approximately 0.54 absorbance units to approximately 1.18 absorbance units, which is consistent with a large proportion of the wax compounds being retained by the membrane during the filtration.
  • a METcell crossflow filtration system (Evonik Membrane Extraction Technology Ltd, UK) containing coupons of DuraMemTM S XP2 organic solvent nanofiltration membrane (Evonik Membrane Extraction Technology Ltd.) was used for this experiment - see Figure 5 for a schematic diagram of the METcell crossflow filtration system.
  • DuraMemTM S XP2 is a silicone-coated membrane prepared according to DE10 2009 047 351 with a nominal molecular weight cut-off of approximately 350 g.mol -1 .
  • the membrane was made ready for use by filtering 200 mL of limonene (Sigma-Aldrich, Germany) through the membrane coupon at ambient temperature and 30 bar filtration pressure to remove the conditioning agent (preservative) from the DuraMemTM S XP2 membrane.
  • limonene Sigma-Aldrich, Germany
  • the filtration cell was emptied and refilled with 500 mL of single-fold orange oil that had been processed with a PuraMemTM S380 membrane according to the methodology of Example 3 to remove wax compounds.
  • the single-fold orange oil was filtered at a temperature of 30 degC and filtration pressure of 30 bar. Samples of the permeate were collected and analysed using an Agilent 6850 gas chromatograph fitted with an FID detector.
  • the gas chromatograph was fitted with an HP-5 column (30 m x 0.25 mm diameter) from Agilent Technologies and subject to the following temperature programme - 70 degC for 1 minute, ramp from 70 degC to 250 degC at 30 degC.min -1 , ramp from 250 degC to 310 degC at 20 degC.min -1 , hold 310 degC for 2 minutes.
  • the injector temperature was 275 degC and the detector temperature was 350 degC.
  • Table 1 shows the membrane rejection values for a select number of compounds in the oil calculated from the analytical results obtained from the gas chromatograph (rejection is defined above in Equation 1).
  • Table 1 - Rejection of select compounds in single-fold orange oil when filtered with DuraMemTM S XP2 membrane Compound Rejection (%) Limonene 0 Decanal 0 Geranial 0 Valencene 0 ⁇ , ⁇ -sinensal 60 Waxes, colour compounds, etc. >95%
  • PuraMemTM S380 is a silicone-coated membrane prepared according to DE10 2009 047 351 with a nominal molecular weight cut-off of 600 g.mol -1 .
  • the membrane was prepared by filtering 5 L of limonene (Sigma-Aldrich, Germany) at ambient temperature and 30 bar filtration pressure to remove the conditioning agent (preservative) from the PuraMemTM S380 membrane.
  • a dead-end METcell filtration cell (Evonik Membrane Extraction Technology Ltd, UK) containing a coupon of DuraMemTM S XP2 organic solvent nanofiltration membrane (Evonik Membrane Extraction Technology Ltd.) was used for this experiment - see Figure 1 for a schematic diagram of the METcell dead-end filtration system.
  • DuraMemTM S XP2 is a silicone-coated membrane prepared according to DE10 2009 047 351 with a nominal molecular weight cut-off of approximately 350 g.mol -1 .
  • the membrane was prepared by filtering 200 mL of limonene (Sigma-Aldrich, Germany) through the membrane coupon at ambient temperature and 30 bar filtration pressure to remove the conditioning agent (preservative) from the DuraMemTM S XP2 membrane.
  • the data shows that by applying the lower molecular weight cut-off membrane DuraMemTM S XP2 additional removal of pesticides (agrochemical residues) can be achieved.
  • This example demonstrates the potential to remove agrochemical residues from essential oil, including five-fold orange oil.
  • this example demonstrates the potential benefits of processes sequentially applying more than one selectively permeable membrane to address a given separation task.

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Claims (15)

  1. Verfahren zur Trennung von Komponenten eines ätherischen Öls, das ein aus Pflanzenmaterial gewonnenes, hydrophobes, nicht-lipidisches natürliches Öl ist, das weniger als 40 Gew.-% Lipide enthält, wobei das Verfahren umfasst:
    (i) Bereitstellen eines ätherischen Öls, wobei
    das ätherische Öl aus einem natürlichen Ausgangsmaterial pflanzlichen Ursprungs durch Dampfdestillation oder aus dem Epikarp von Citrusfrüchten durch mechanische Verfahren oder durch Trockendestillation erhalten wird, gefolgt von Abtrennen der wässrigen Phase, falls vorhanden, durch physikalische Verfahren,
    oder
    das ätherische Öl durch mechanisches Auspressen von Pflanzenmaterial, das von Citrusfrüchten verschieden ist, gewonnen wird,
    oder
    das ätherische Öl durch Extraktion des Pflanzenmaterials mit überkritischen Lösungsmitteln, vorzugsweise überkritischem CO2, gewonnen wird,
    (ii) Bereitstellen einer selektiv permeablen Nanofiltrationsmembran mit einer ersten Oberfläche und einer zweiten Oberfläche;
    (iii) Auftrennen des ätherischen Öls durch Überführen von einer oder mehreren Komponenten des ätherischen Öls durch die Membran von der ersten Oberfläche zu der zweiten Oberfläche durch Inkontaktbringen des ätherischen Öls mit der ersten Oberfläche,
    wobei das Öl in Kontakt mit der ersten Oberfläche ein Retentat bildet und das Öl in Kontakt mit der zweiten Oberfläche ein Permeat bildet,
    wobei der Druck an der ersten Oberfläche höher als der Druck an der zweiten Oberfläche ist,
    und wobei die Konzentration der einen oder mehreren Komponenten des ätherischen Öls in dem Öl in Kontakt mit der ersten Oberfläche gegenüber dem ursprünglichen ätherischen Öl verringert ist.
  2. Verfahren gemäß Anspruch 1, wobei das Retentatöl und/oder das Permeatöl zusätzlich mindestens einem weiteren Verarbeitungsschritt unterzogen wird.
  3. Verfahren gemäß Anspruch 2, wobei das Retentatöl und/oder das Permeatöl zusätzlich mindestens einem weiteren Kontakt mit einer selektiv permeablen Membran, vorzugsweise einer Nanofiltrationsmembran, unterzogen wird, wobei vorzugsweise zwei unterschiedliche Membranen mit zwei unterschiedlichen Molekulargewichtsgrenzen verwendet werden, wobei besonders bevorzugt mindestens eine Membran mit einer Molekulargewichtsgrenze von zwischen 400 g.mol-1 und 1500 g.mol-1, insbesondere zwischen 500 g.mol-1 und 800 g.mol-1, und mindestens eine Membran mit einer davon verschiedenen Molekulargewichtsgrenze von zwischen 150 g.mol-1 und 600 g.mol-1, insbesondere zwischen 200 g.mol-1 und 500 g.mol-1, verwendet werden.
  4. Verfahren gemäß einem der vorstehenden Ansprüche,
    wobei das ätherische Öl aus Pflanzen stammt und ausgewählt ist aus Ölen, die aus Beeren, Samen, Rinde, Holz, Rhizom, Blättern, Harz, Blüten, Schale und Wurzeln hergestellt wurden,
    und/oder
    wobei das ätherische Öl aus der Gattung Citrus stammt
    und/oder
    wobei das ätherische Öl ausgewählt ist aus Ölen, die aus Süßorange, Orange, Zitrone, Limette, Grapefruit, Bergamotte, echter Limette, Pomelo, Limone, Mandarine, Tangerine, Bitterorange, Rangpur, persischer Limette, Klementine, Yuzu, Kaffir-Limette, Ugli stammen,
    und/oder
    wobei das ätherische Öl ausgewählt ist aus Pimentöl, Wacholderöl, Kreuzkümmelöl, Zimtrindenöl, Campheröl, Rosenholzöl, Ingweröl, Basilikumöl, Eukalyptusöl, Zitronengrasöl, Pfefferminzöl, Rosmarinöl, Grüne-Minze-Öl, Teebaumöl, Weihrauchöl, Kamillenöl, Nelkenöl, Jasminöl, Lavendelöl, Rosenöl, Ylang-Ylang-Öl, Bergamottenöl, Grapefruitöl, Zitronenöl, Limettenöl, Orangenöl und Baldrianöl.
  5. Verfahren gemäß einem der vorstehenden Ansprüche, wobei das Verfahren eine Verringerung
    im Wachsgehalt
    und/oder
    der Farbe
    und/oder
    von mindestens einer natürlichen und/oder synthetischen Verunreinigung ausgewählt aus Umweltschadstoffen, agrochemischen Rückständen, aus Verpackungen extrahierbaren Stoffen, Wachsen, Pflanzensterolen, lipophilen Hormonen, gefärbten Komponenten, Oxidationsprodukten, Komponenten, die einen unerwünschten Geruch und/oder Geschmack in dem Ölgemisch erzeugen, oder Vitaminen
    in dem hergestellten ätherischen Öl bewirkt im Vergleich zu dem ursprünglichen ätherischen Öl.
  6. Verfahren gemäß Anspruch 5, wobei die mindestens eine natürliche oder synthetische Verunreinigung agrochemische Rückstände umfasst.
  7. Verfahren gemäß einem der vorstehenden Ansprüche, wobei das Retentat eine erhöhte Konzentration von mindestens einer Komponente des ätherischen Öls, ausgewählt aus Vitaminen, Pflanzensterolen, lipophilen Hormonen, gefärbten Komponenten, Furanocumarinen, Sesquiterpenen im Vergleich zu dem Fettsäure-Öl-Gemisch aufweist.
  8. Verfahren gemäß einem der vorstehenden Ansprüche, wobei die mindestens eine selektive Nanofiltrationsmembran ein Material ausgewählt aus Polyethylen, Polypropylen, Polytetrafluorethylen (PTFE), Polyvinylidendifluorid (PVDF), Polysulfon, Polyethersulfon, Polyacrylnitril, Polyamid, Polyimid, Polyamidimid, Polyetherimid, Celluloseacetat, Polyanilin, Polypyrrol, Polyetheretherketon (PEEK), Polybenzimidazol und Gemischen davon umfasst.
  9. Verfahren gemäß Anspruch 8, wobei die mindestens eine selektive Nanofiltrationsmembran ein Polyimid umfasst, vorzugsweise ein nachträglich vernetztes und mit einer schwach flüchtigen Verbindung imprägniertes Polyimid.
  10. Verfahren gemäß einem der vorstehenden Ansprüche, wobei die mindestens eine selektive Nanofiltrationsmembran ein Verbundmaterial ist, das einen Träger und eine dünne, selektiv permeable Schicht umfasst, vorzugsweise eine dünne, selektiv permeable Schicht umfassend ein Material ausgewählt aus Elastomeren auf Basis modifizierter Polysiloxane einschließlich Elastomeren auf Polydimethylsiloxan(PDMS)-Basis, Elastomeren auf Ethylen-Propylen-Dien(EPDM)-Basis, Elastomeren auf Polynorbornenbasis, Elastomeren auf Polyoctenamerbasis, Elastomeren auf Polyurethanbasis, Elastomeren auf Butadien- und Nitrilbutadienkautschuk-Basis, Naturkautschuk, Elastomeren auf Butylkautschukbasis, Elastomeren auf Polychloropren(Neopren)-Basis, Epichlorhydrinelastomeren, Polyacrylatelastomeren, Polyethylen, Polypropylen, Polytetrafluorethylen (PTFE), Elastomeren auf Polyvinylidendifluorid(PVDF)-Basis, Polyetherblockamiden (PEBAX), Polyurethanelastomeren, vernetztem Polyether, Polyamid, Polyanilin, Polypyrrol und Gemischen davon, besonders bevorzugt eine dünne, selektiv permeable Schicht umfassend ein Elastomer auf Polysiloxanbasis.
  11. Verfahren gemäß einem der vorstehenden Ansprüche, wobei die mindestens eine selektive Nanofiltrationsmembran ein anorganisches Material ausgewählt aus Siliciumcarbid, Siliciumoxid, Zirkoniumoxid, Titanoxid und Zeolithen umfasst.
  12. Verfahren gemäß einem der vorstehenden Ansprüche, wobei die mindestens eine selektive Nanofiltrationsmembran eine Polymermembran mit dispergierten organischen oder anorganischen Matrizen in der Form von pulverförmigen Feststoffen umfasst, die in Mengen von bis zu etwa 20 Gew.-% der Polymermembran vorhanden sind.
  13. Verfahren gemäß einem der vorstehenden Ansprüche, wobei die mindestens eine selektive Nanofiltrationsmembran siliconbeschichtete organophile Nanofiltrationsmembranen umfasst, vorzugsweise auf der Basis von Polyimid-Nanofiltrationsmembranen.
  14. Verfahren gemäß einem der vorstehenden Ansprüche, wobei mindestens eine selektive Membran eine Molekulargewichtsgrenze im Bereich von etwa 150 g/mol bis etwa 1.500 g/mol, vorzugsweise von etwa 200 g/mol bis etwa 800 g/mol und insbesondere von 200 g/mol bis kleiner als oder gleich 600 g/mol, aufweist.
  15. Verfahren gemäß einem der vorstehenden Ansprüche, wobei das Nanofiltrationsverfahren bei einer Temperatur im Bereich von etwa 10 °C bis etwa 50 °C und/oder mit einem Transmembrandruck im Bereich von etwa 10 bar bis 60 bar durchgeführt wird.
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PH12014502480A1 (en) 2015-01-12
AU2013258396B2 (en) 2017-07-06
PH12014502480B1 (en) 2015-01-12
EP2846900A1 (de) 2015-03-18
AU2013258396A1 (en) 2014-11-06
CN104302384A (zh) 2015-01-21
CN104302384B (zh) 2017-04-12
ES2804454T3 (es) 2021-02-08
MX2014013474A (es) 2015-05-07
US10934501B2 (en) 2021-03-02
US20190106654A1 (en) 2019-04-11
JP2015521219A (ja) 2015-07-27
BR112014027647B1 (pt) 2020-12-22
CA2872721C (en) 2019-04-30
BR112014027647A2 (pt) 2017-06-27
US20150118331A1 (en) 2015-04-30
CA2872721A1 (en) 2013-11-14
US10202562B2 (en) 2019-02-12
MY185143A (en) 2021-04-30
WO2013167307A1 (en) 2013-11-14
EP3677328A1 (de) 2020-07-08
SG11201406975XA (en) 2014-11-27

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